JPS58125605A - Method of recovering hydrogen - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The need for 0% hydrogen to be used in refining operations has become illegal and has become an urgent problem. More efficient methods of recovering hydrogen from exhaust gas streams are currently needed.

In various cases, solid adsorbents are used to selectively separate hydrocarbons such as methane, ethane, etc. and other non-polar and polar compounds such as nitrogen, carbon monoxide, carbon dioxide, etc. from hydrogen. It is disclosed in the literature. V) Adsorbents disclosed in the literature for this purpose generally include activated carbon, activated bauxite, activated alumina, silica gel, silica alumina, synthetic zeolites and so-called charcoal molecular sieves. A complete cycle of operation in a selective absorption process generally requires regeneration of the depleted solid adsorbent, and continuous operation requires that the adsorption device be cycled between adsorption and desorption processes; Preferably, both adsorption and desorption are performed in parallel. The adsorbed material can be removed from the adsorbent solid without changing temperature or pressure by purging the adsorbent solid with an inert gas or by contacting the adsorbed material with a more strongly adsorbing compound. It can be removed from the adsorbent solid by release. However, thermal or pressure swing techniques are generally used to regenerate the adsorbent.

In the thermal fluctuation method, a solid bed of adsorbent is heated sufficiently to a temperature higher than the temperature at which the adsorbent bed was used for the adsorption process to reduce the adsorption tendency of the adsorbent material, and the adsorbent material is then passed through a purge gas stream. It can be removed by In the pressure swing method, the ambient pressure on the adsorbent solid is optically reduced to a power lower than the pressure at which the adsorbent bed was used in the adsorption process, reducing the adsorbent's O uptake capacity; can be removed by a purge gas stream.

Most selective adsorption methods involve contacting a fluid, particularly a gas or steam, with a bed of ground solids, and the bed! 7) contacting one or more with a gas or vapor to selectively separate compounds from the gas in an adsorption step, while desorbing the adsorbed compounds in one or more of the other beds; Regenerate solids. Although fixed beds of adsorbents are the most common, the use of fluidized beds overcomes the added drawbacks of fixed bed operation, namely extensive valve and manifold equipment.

and heat waste due to cyclical heating and cooling of the flow path, vessel walls, and internal vessel components.

However, fluidized bed adsorption processes eliminate or reduce the need for valve and manifold equipment, facilitate the movement of the bulk, and provide better heat transfer properties primarily due to solids circulation and solids pack mixing. Nevertheless, it is subject to restrictions. In fact, it has been found that this last characteristic, namely ensuring good heat transfer conditions and isothermal conditions within the fluidized bed itself, is itself a drawback in adsorption systems. Therefore, solid O back-mixing with H
To reduce the amount of adsorbent, vertically spaced shallow moving beds are generally used to provide staged contact between the gas and the adsorbent. The complexity introduced into the #L moving bed suction method for such staging precludes the more general use of #LwJ beds for selective separation in gas processing.

U.S. Permit No. 4.283.204 specifies that R.
U.S. Pat. No. 4,115,927, issued September 26, 1978 to E. Rosenweig, discloses a method for separating contaminants from gas using a magnetically stabilized fluidized bed. has been done. Adsorption and desorption of contaminants from the feed takes place in a fluidized (expanded and floated) bed, which consists of a plurality of vertically spaced Achieved without requiring shallow beds. Beds so stabilized have many of the appearance and physical properties of fixed beds, without significant circulation of qualitative solids (other than slow plug flow of solids through the vessel),
There is very little gas bypass, if any. magnetic 4o
The use allows the use of a surface fluid flow velocity of 2% 5.1° or 20 times or more than the superficial fluid flow velocity of the fluidized bed in the initial fluidization without aSS application and in the absence of bubbles. do. As the superficial fluid velocity increases, the pressure drop across the bed becomes similar to that expected from a conventional fluidized bed without the application of a magnetic field, and at minimum fluidization velocity the pressure drop across the bed becomes ~1. , then remains relatively at -W as the fluid velocity increases. This stable fluidized bed condition persists even if, for example, the solids move continuously in a substantially downward plug flow through the contact vessel.

A stepwise countercurrent flow of solids to the gas flow used to fluidize the bed is achieved, resulting in overall capital and operating cost savings compared to conventional methods. In addition, better particle retention than in the case of magnetic particles under the action of an applied magnetic field allows for the use of smaller particles, which results in better heat and mass transfer than the amount of reactant Q].

Although this provides a foolproof method for separating contaminants from gases, further improvements are desirable and needed.

Therefore, the primary object of the present invention is to provide a new and improved method for the recovery and production of hydrogen by selective adsorptive separation of non-hydrogen components from an aqueous-containing exhaust gas stream using the application of a magnetic field. The purpose is to provide a method.

This objective is achieved according to the invention by an improved adsorption process for more efficient recovery of hydrogen from hydrogen-containing feeds, in which the particulate adsorbent solid is endowed with a magnetizable component and is made non-magnetizable. The adsorption zone selectively adsorbs hydrogen components and concentrates hydrogen in the exhaust gas, and the desorption zone desorbs the adsorbed material by heat fluctuation operation or heat/partial pressure fluctuation operation of the granular adsorbent solid, and the granular Regenerate adsorbent solids.

Upon cooling and recirculation to the 01J adsorption zone, (
a) directing said feed in the adsorption zone preferably adiabatically to a downwardly moving fluidized bed of particulate adsorbent solids;
L fine contact to magnetically stabilize the Ail marking bed to inhibit large circulation of adsorbent solids within said bed;
adsorbing hydrocarbons from the feed on the bed and leaving the magnetically stabilized adsorption zone with a dehydrocarbonized gas stream having a water content greater than that contained in the feed entering the magnetically stabilized adsorption zone; (b) extracting the hydrocarbon-enriched hydrogen-containing particulate IJ & reagent solids from the magnetically stabilized adsorption zone and transferring them to a hydrogen displacement zone; The particulate adsorbent solids contained therein are passed in a plug flow and contacted with the hydrocarbon gas to provide sufficient countercurrent contact of the MU adsorbent solids to substantially expel the hydrogen, and the expelled hydrogen into the adsorption zone. move it,
and is particularly improved by an adsorption/hydrocarbon displacement operation characterized in that particulate adsorbent solids containing dehydrogenated hydrocarbons are removed from the hydrogen displacement zone and transferred to a desorption zone.

In the magnetically stabilized bed adsorption step (a) described above, the feed is injected into the bottom of the zone and flows in the direction of a slowly descending stable fluidized bed of adsorbent, and the gas flows through this zone. (a magnetic field is applied in the same direction as the gravitational field), rising at a velocity sufficient to cause unexpansion and fluidization.

l1tlK rising to the top of the bed increases its hydrogen content. Conversely, the percent adsorbent solids hydrocarbon gas increases as the solids descend to the outlet side of the bed. Preferably the two particulate wicking solids have a temperature of from about 40 to about 300'F, preferably from about 130'F to about 300'F.
It enters the adsorption zone 1 at a temperature in the range of about 250 DEG C. and above and exits the adsorption zone at a temperature of about 10 to about 150 degrees below, preferably about 10 to about 100 degrees above, the temperature of the incoming particulate adsorbent solids. This is because adsorption is an exothermic reaction, depending to some extent on the nature of the adsorbent and the adsorbent solids. In typical operations using suitable adsorbent solids, i.e., magnetite 5A molecular conjugates and magnetite activated carbon conjugates, the particulate adsorbent solids enter the zone at a temperature below about 200°C, which is exothermic. Approximately 260″F at the gas inlet point due to the heat of reaction
rises to.

In the hydrocarbon displacement step (b), the bed of hydrocarbon-rich granular adsorbent solids removed from the adsorption zone is contacted with a hydrocarbon gas stream, suitably a recycled hydrocarbon gas stream from the step (7). and the hydrocarbon gas flow is at the bottom of this zone Kf
As the granular adsorbent is consumed, hydrogen is expelled from the interstices and pores of the solid, and each type of hydrocarbon gas added is equal to the volume of gas emitted, i.e. hydrogen and the remaining particles contained in the interstices and pores Approximately equal to the total volume with the feed gas components.

When hydrogen is exchanged in this way, almost no hydrogen flows out of the zone together with the adsorbent solid, and an interface is formed so that almost no hydrogen exists below the sled. The particulate adsorbent solids removed from the zone are substantially free of hydrogen, which increases overall hydrogen recovery.

When the adsorbent solids are introduced as a falling bed into the hydrogen displacement zone, moved as a plug flow and brought into co-current contact with the hydrocarbon gas, the upper part of the hydrogen displacement zone is such that the plug flow solids in countercurrent contact flow from the adsorption zone into this zone. operated at inlet temperatures and outlet humidity generally from about 10 to about 100 below, usually from about 20 to about 50
“F rises.

When using the preferred magnetic 5A molecular sieves and magnetic activated carbon described above, the outlet temperature will typically be about 60" F below the solids inlet temperature. Preferably, heat is applied to create the temperature gradient. I can't give it.

The temperature at the bottom of the floor is about 60 to about 450 degrees Fahrenheit higher than the temperature at the top of the floor.
, preferably operating at a temperature in the range of about 160 to about 350''F.

In another preferred aspect, the hydrogen displacement zone is operated by applying a magnetic field sufficient to stabilize the downflowing fluidized bed of particulate adsorbent solids to bring the bed into self-current contact with the hydrocarbon gas. The floor temperature at the top is about 50 to about 4
00"F, preferably in the range of about 150" to about 300"F, with the bottom of the bed being about 60" to about 450" below the top bed temperature.
"F, preferably from about 160 to about 350" FI7) temperature. The temperature gradient maintained in the bed causes nearly all trace amounts of hydrogen to escape from the particulate adsorbent solids exiting the bed.

The desorption, or regeneration phase of the operation is initiated by transferring the dehydrogenated hydrocarbon-containing particulate adsorbent solids to the desorption zone (c). In this desorption zone (e),
forming a fluidized bed of the dehydrogenated hydrocarbon-containing particulate solid and heating it at a temperature sufficient to desorb the hydrocarbons from the particulate solid, removing the hydrocarbons from the zone;
The particulate adsorbent solids containing at least residual hydrocarbons are then transferred to a stripping zone and the hydrocarbons are stripped therefrom by stripping, suitably contacting with hydrogen. Preferably, however, the hydrocarbons are stripped from the adsorbed solid by stripping with steam. In the steam stripping zone (d), the particulate adsorbent solids containing residual hydrocarbons can be formed as a moving slumbed, but are preferably formed as a fluidized bed and magnetically stabilized. The bed is brought into countercurrent contact with water vapor to desorb and largely eliminate residual hydrocarbons while suppressing large circulation of adsorbent solids within the bed.

The desorption of zero hydrocarbons from the dehydrogenated hydrocarbon-containing particulate adsorbent solids at the internal pressure of desorption zone (c) described above is carried out at a desorption temperature of about 300 to about 600 degrees F, preferably about 3
It is carried out in a heated fluidized bed to a temperature in the range of 50 to about 450" F!r). Heat is generally supplied by a heat exchanger, such as a coil mounted within the solid fluidized bed, through which the heat is supplied. Passing a pressurized thermal fluid (usually water vapor).The partially desorbed solids are transferred from the desorption zone to the hydrocarbon stripping zone (a), into which water vapor is directly injected to maintain the desorption temperature; At the same time, it strips hydrocarbons by adsorption and fractionation.

The adsorbent solid is heated due to the adsorption of at least part of the water.

Usually, the temperature of the desorption zone is about 300 to about 600? , preferably in the range of about 350 to about 450'F. The wet particulate solids are then transferred to a steam displacement or water removal zone, which preferably includes the following step sequence: That is, first, hydrogen is used to expel water vapor from the interstices and pores of the solid;
The water is then stripped from the adsorbent solids while the adsorbent particles undergo evaporative cooling in a fluidized bed cooling zone before being recycled to the adsorption zone.

Preferably, the sequence of steps is to remove the water and then cool the adsorbent particles. In this first step, the product hydrogen is used to force water vapor out of the interstices and pores of the granular adsorbent particles.

Hydrogen is in countercurrent contact with the adsorbent particles at a rate approximately equal to the volume of water vapor or water within the interstices and pores. When replacing water vapor in this way, most of the water vapor and gaseous hydrocarbons are not entrained in the water removal step where the water on the adsorbent particles is removed. The steam displacement step minimizes the amount of stripping steam required in the hydrocarbon stripping zone (d) by more effectively utilizing the steam injected into the zone.

Additionally, the steam displacement step prevents residual gaseous hydrocarbons remaining within the interstices or pores of the adsorbent particles from contaminating purified hydrogen that is recovered downstream in further operating steps.

In the second step of the water removal/cooling zone, the evaporative cooling step, the adsorbent particles are injected into the bottom of the process at a rate sufficient to strip nearly all of the water from the adsorbent particles. brought into countercurrent contact with hydrogen. The removal of water is
The adsorbent particles are about 600 to about 550 below, preferably about 35
From inlet temperatures ranging from 0 to below about 450, from about 200 to about 5
evaporative cooling to an exit temperature in the range of below 0.000, preferably from about 250 to about 350 below. Then, the dried adsorption ^11
The solid is transferred to a cooling zone to adjust the temperature of the solid to the adsorption temperature.

The cooling zone is a zone in which a fluidized bed of exogenous particulate adsorbent solids is established and maintained in a heat exchange relationship with the coolant, preferably cooling water, to reject heat to the cooling water. In the fluidized bed cooling zone, the temperature of the adsorbed A1 solid is increased to the desired adsorption temperature vI
4, and then transferred to an adsorption device.

In a preferred mode of operation, these several zones are used to provide a continuous, single temperature swing adsorption/desorption step utilizing countercurrent plug flow of adsorbent and gas, which is less than K. It is possible to use particle size adsorbents to provide faster adsorption-desorption rates and to provide a fluidized bed heat transfer zone that provides optimal processing and strategy to planar conditions. This type of identification method, which provides high recoveries (e.g., >95%) of aqueous systems of high purity (e.g., >95%), utilizes an adiabatic, magnetically stabilized adsorption moiety to provide countercurrent contact; Almost complete evacuation of the feed gas from the adsorbent body is obtained; the stripping is carried out using a first desorption process using a fluidized bed to heat the adsorbent solids to a discharging vorticity and a water stream. and a second desorption section supplying heat of adsorption; a stepwise water removal/cooling section, and a stepwise water removal/cooling section; In the first process, hydrogen is used to drive out water vapor and residual gas carbonization particles from the interstices and pores of the granular adsorbent solid, and in the second step, water is removed from the adsorbent solid to generate cooling. Then, in the sixth culm, cooling is further performed in a fluidized bed to the adsorption temperature.

Separation is performed at feed gas pressures ranging from about 50 pounds per square inch gauge pressure (paig) to about 1200 pmig.
, preferably at a pressure in the range of about 200 to about 700 psig, with the fuel gas returned at approximately the feed gas pressure. High purity and crystal recovery are obtained using countercurrent flow of the feed gas.

These and other percentages will be better understood from the following more detailed description of the invention of a particularly preferred embodiment, with reference to the drawings.

The drawing shows a simple flowchart showing how to
1 shows a preferred magnetically stabilized bed temperature swing hydrogen recovery adsorption-dispersion apparatus M, 10 used for the recovery of aqueous systems from gaseous mixtures of hydrogen and hydrocarbons from shoes.

Most of the cyclone separator, floor level, compressor, pump, and other auxiliary equipment have been omitted from the drawing to simplify the figure.

Referring to the drawings, first of all, the device 10 necessarily includes an sorption or adsorption section and a desorption section, and in this example, the adsorption section of the device is located at or near the bottom K of the container. , it will be appreciated that the detachable part is located at the top of the container. On the one hand, the adsorption part (1) of unit #10 thus comprises an upper cooling part 11, an adsorption part 12 into which a hydrogen-containing feed gas or steam is introduced on the lower side, and a hydrogen displacement part 13. On the other hand, the desorption part (2) of the device 10 comprises a desorption part 14, a stripping part 15 and a water removal part 16. In this device 10, the hydrogen adsorbed in the adsorption part of the device is discharged, which is composed of an aqueous/hydrocarbon mixture that flows upward by an adsorbent solid in which the hydrocarbons move downward;
The dehydrogenated adsorbent solids enriched in the hydrocarbon system are then transferred to the desorption section of the apparatus for hydrocarbon extraction and recovery, regenerating the adsorbent solids and obtaining a hydrogen product. Furthermore, it is quite obvious that the adsorption section (1) and the desorption section (2) of the device could be arranged alternately with each other, or the operations could be carried out in separate containers. For example, a convenient alternative arrangement includes (1) a first vessel that includes an intermediate level adsorption section 12 and a lower displacement section 13 that introduce gaseous feed into the upper cooling section 11 and the lower section; A second vessel comprising a desorption section 14, an intermediate stripping section 15 and a water removal section 16, in which the solids are removed from each vessel using a process gas, i.e. hydrogen or hydrocarbons, respectively. Raise to 1 day.

The operation and functioning of each of these parts K, starting from the adsorption section or "sorption side" of the device, is as follows.

Adsorption section 12 is operated adiabatically and contains a magnetically stabilized bed of adsorbent solids. This further provides that the bed is downwardly flowing or moving downward, and that the bed of particulate adsorbent solids is preferably a magnetic activated carbon or molecular sieve composite. Therefore, the bed is stably converted into 'FMh' by raising the gas, and is also subjected to the action of the magnetic field generated by the coil magnet 121 attached concentrically from the outside around the wall of the container, in which case the gas is Distributor 12. and a hydrocarbon stripping gas flowing upwardly from the hydrocarbon displacement section 15. Thus, gas with a relatively low aqueous content enters the bottom of this section and flows countercurrently to the steadily fluidized, slowly descending adsorbent solids. As the gas flows upwardly through the bed of adsorption section 12, hydrocarbon systems and other non-hydrogen components are adsorbed onto the adsorbent solids. Adsorption of hydrocarbons generates heat, so that the solids introduced into the adsorption section 12 are cooled by a predetermined amount in the cooling section 11 before being introduced into the adsorption section 12.

Cooling of the adsorbent solids in the cooling section 11 before introduction into the adsorption section 12 brings the particulate adsorbent solids into a dynamic state VC.
This is achieved by maintaining and obtaining good heat transfer in the cooling curve. The bed of stable fluidized adsorbent positioned above the grid 11 is cooled, for example, by using a heat transfer coil 113 located in a vessel and passing cooling water therethrough during operation. If desired, a filter can be provided above the top of the bed by employing magnetic field coils 111 surrounding the exterior of the upper vessel above the bed surface. The cooled adsorbent solids overflow the weir 114 and are introduced into the adsorption section 12, and the downwardly moving adsorbent solids are regenerated fresh from the water removal section 16 of the desorption section of the apparatus in the bed of the cooling section 11. Replenishment with adsorbent solids. The solids that have left the adsorption section 12 overflow the distributor 12 and move downward through the passage 123 to the hydrogen displacement section 15.
flow inside.

The hydrogen ttm portion 15 is the key point of the method and is the discipline → ridge. A circulating hydrocarbon-based gas is introduced into this section to displace and discharge the aqueous system from the interstices and pores of the spent adsorbent solid. Therefore, the solids transferred from the stratified portion 12 contain a relatively large amount of hydrogen within the crevices or between the adsorbent solid particles and within the pore volume of the adsorbent solids. is unavoidable, and to the extent that an aqueous system is present in the adsorbent solids transferred to the desorption section 14, this is wasted as it is contaminated by the gases escaping from the yarn during regeneration of the sorbent cut solids. Therefore, the adsorbent solid can be directly transferred to the desorption part 1.
If removed in step 4, this hydrogen is stripped from the hydrocarbon XK and flows out of the apparatus together with the desorbed gas, resulting in a reduction in hydrogen recovery. Therefore, during operation of the displacement section 16, a volumetric portion of the hydrocarbon product is routed substantially equal to the volume of the aqueous and residual feed scum components contained within the voids and pore volumes of the adsorbent solids. In addition to the distributor 162 by 18, the hydrogen contained in the interstitial and pore volumes of the adsorbent solid is exchanged as completely as possible, and it is bathed or drained from the trap via the distributor 15 and the channel 133. and ensures that the adsorbent solids captured by the scrubbing hydrocarbon lift gas which also exits the displacement portion 16 via path 19 are substantially free of hydrogen.

In the preferred operation of the aqueous direct exchange section 13, the incoming adsorbent solid particles are transferred to the path 18 without the application of a stabilizing magnetic field.
The plug flow moves countercurrently to the upward flow of circulating hydrocarbons introduced by the pump. Thus, the adsorbent solid particles continue to fall or move close to each other as the hydrogen is purged, aiding in the release of hydrogen. By regulating the flow of the circulating hydrocarbon bulk flow, a boundary is formed within this section, below which the downwardly moving solids are substantially free of hydrogen. In another preferred operation, the adsorbent solid particles in the stripping section 13 can be stabilized as a bed by the application of a magnetic field to assist in the transport and movement of the particles from this section.

In this embodiment, removal of water volume from the purged solids is facilitated by establishing a temperature gradient between the bottom and top of the bed. Preferably, the stable fluidization allows low level heat from a suitable source to be exchanged with the 10 parts of the bed, and also moves the return heat (i.e. higher temperature) from a suitable source downwards. It can exchange heat with the bottom of the floor.

In the first part of the desorption cycle, the adsorbent solids are heated to the desorption temperature in a fluidized bed to desorb some of the hydrocarbons, the remaining hydrocarbon system is removed in a steam stripping section 15, and the water is then removed from the aqueous system. removed from the adsorbent solids by treatment with .

Adsorbent solids that are mostly or completely saturated with hydrocarbons but completely K or almost free of aqueous systems are captured at the discharge from path 19 and sent to desorption section 14 via solids return path 20 .
Rise and feed inside. The bed of adsorbent solids contained therein is fluidized to improve heat transfer between the adsorbent solids, and the bed is fluidized by the humid gas rising through the grid 142 on which it rests. Preferably, the filter is maintained above the bed to inhibit the escape of solids from the top of the bed. For example, the use of magnetic coils 141 allows the magnetic field to be maintained well above the top level of the floor.

The bed is heated by passing steam through an internal heat exchange coil 143.

Heating the adsorbent solid causes interstitial gases to exit the solid through desorption and thermal expansion, and the moist rising gas introduced into the desorption section 14 promotes the release of hydrocarbon systems.

The desorbed hydrocarbons exit the desorption section 14 via path 21 together with the humid gas. The effluent gas is heat exchanged and fed into a knockout pot to remove water, and the uncondensed gas is recovered as a hydrocarbon product from line 22, while a portion thereof is recycled via line 23.20. The partially regenerated adsorbent solids are transferred to the steam stripping section 15 via the overflow weir 144 and circulated as adsorbent solid gas and hydrogen replacement gas in the hydrogen displacement section 13. Remove further.

The partially regenerated adsorbent solids transferred from the desorption section 14 into the IJ Zubing section 15 are transferred to the distributor 15.
2 is introduced into the fluidized bed by gas pressure from below. A stabilizing field is applied to the fluidized bed, for example by means of an externally mounted magnetic coil 15□.

Steam is injected into the bed via path 153, which contaminately purges the hydrocarbon system from the pores of the adsorbent solids and heats the dehydrated adsorbent solids. This heated, dehydrated adsorbent solids overflows distributor 152 and passes through path 154 to a series of staged water removal zones.
In this case, the first zone of the two-stage zone [inflows]. In this first zone, water vapor is forced out of the interstices and pores of the adsorbent solid particles by the aqueous system to provide better heat utilization and to suppress contamination of the product hydrogen by hydrocarbons.

The wet decarburized adsorbent solids pass through distributor 152 and thus flow into a downwardly moving falling or descending bed of material. The formed bed contacts hydrogen that is introduced into distributor 155 via path 163. Most of the water vapor is now forced out of the interstices and pores of the adsorbent solid, which means that most of the hydrocarbons are removed from the secondary
Prevents contamination of the product hydrogen as may occur when transferred to the water removal stage. The partially softened adsorbent solids overflow the bed via passage 156 of distributor 15S and
It enters the second water exchange or water removal zone or water removal section 16 via dipleg 157 . In this second zone, the partially dried adsorbent solids are fluidized by hydrogen injected from path 164 through distributor 16, and the fluidized bed is formed by a magnetic field generated by an externally mounted magnetic coil 1 (S). The injected aqueous system removes nearly all residual water from the adsorbent solid particles.The dried regenerated absorbent solid particles are then passed through the passages 16s of the distributor 162 and the dipleg 166. The wet gas from the water displacement section 16 is transferred via line 24 through a heat exchanger into the water knockout pot and the hydrogen product is withdrawn via line 25.

The invention is further illustrated by the following examples.

For convenience of example, reference is again made to the drawings and to the tables below. The numbers in parentheses refer to tables that show the composition, temperature, flow rate, etc. at different locations in the process.

200 consisting of 75% H2 and 25% hydrocarbon system
The feed stream [1] of Paig is transferred to the adiabatic absorption chamber 12, where the descending granular carbon solids (3 parts mi
% stainless steel powder).

The solids transfer rate is approximately 1.70 Xl 051b/hr. The temperature of the coal thread solids increases as stratification occurs, with the solids at 265″F at the feed inlet rhVc;
Contains 71 bonds of hydrocarbon per 100 bonds of carbon. As the solids fall downward from the feed stream F1, they entrain the feed gas into the interstices between the particles and into the pores within the particles. The feed gas contains a significant amount of water system, and this water W could only be recovered by flowing into the desorption section. The feed gas is thus replaced by an ascending gas stream [8] containing 52% H, which is injected into zone 13 via path 18. Circulating flow [8] is
It is added at exactly the same rate as the downward flow of feed gas that is being entrained by the descending solids. Due to the higher hydrocarbon partial pressure in the displacement zone, additional hydrocarbons are adsorbed and the temperature as the carbon exits the bottom of the vessel via path 19 is below 290°C, resulting in a hydrocarbon load of 96 bonds of hydrocarbons per 100 bonds of carbon. Become.

The solids leaving the column bottom are transferred via path 20 to the desorption section and into the noble section of column 1 via hydrocarbon-loaded gas stream [7]. The solids are heated in the fluidized bed in zone 14 to a desorption temperature below 690°C. A heat exchanger with a condensing stream of 600 paig of steam [15] supplies the necessary flow. A fluidizing gas is supplied directly below the fluidized bed from the stripping section, and this fluidizing gas consists of stripping steam introduced through path 153 and hydrocarbons desorbed in the stripping section. Some desorption occurs at the fluidized bed desorption partial pressure, and the carbon stream exiting this fluidized desorption section (S-9) contains 5.2 bonds of hydrocarbon per 100 bonds of carbon; Contains 12 bonds of adsorbed water.

Most of the residual hydrocarbons remaining in the carbon leaving the fluidized bed are removed in the stripping zone. In the stripping zone, the descending solids come into countercurrent contact with a stream of 200 palg stripping steam [5] introduced via path 153 previously injected directly into the bed. A portion of the water vapor is adsorbed on the carbon. The heat of adsorption of water is almost offset by the deheating of the hydrocarbons, and the temperature of the solids exiting the IJ Zübbing vessel is 400 °C via path 157.
°F. These solids contain 11 carbon per 100 bonds.
Contains bond hydrocarbons and 58 pounds of H2O.

As the solid passes through the steam injection point, it entrains the steam into the interstices and pores. The water vapor in the interstices and pores would not be utilized if it were transported downwards with the solids. The water vapor is therefore replaced by the H2 stream [3] introduced by path 163. As in the adsorber displacement section, the hydrogen flow [5] is applied in such a way that it is exactly equal to the downflow of water vapor that is being entrained in the down-dip voids between the particles and into the pores of the particles.

The carbon leaving the stripping zone contains adsorbed water, which is removed in the adiabatic water removal zone 16. In this zone, the aqueous stream [2] from the cooling zone 11 comes into countercurrent contact with the carbon to strip the water from the carbon. Removal of water causes the solids to evaporatively cool from 400"F to below 300" K. Countercurrent contact with H2 in the evaporative can further strips the hydrocarbon system from the carbon, resulting in evaporative cooling via the dipleg 166. The solid stream [5-11] exiting the cooler contains a4 bonds of hydrocarbon system and 0.6 bonds of H, O per carbon bond.

The hydrocarbon system removed in the evaporative cooler exits IAI along with the 4F product aqueous stream [4], resulting in a 964% pure H2 product. Lower or higher purity products may be obtained by increasing the water evaporation 1 stripping rate, i.e., stream [5] to IAI tx to leave more or less hydrocarbons in the carbon exiting the stripper. Le Lou.

Further solids operation from 300"F" to 2001' is carried out in fluidized bed cooler 11. 1232 gallons/
The solid is cooled by heat exchange with the cooling water for one cycle. The H2 product scum flows upward from the adsorber through the grid as ωL[G-12], resulting in mobilization of t)1. Cooled to 200”F & 1ffi1
The body [S-12] flows into the adsorber again.

Flow MSCF/D 10 7.6 0,96 7
．． 7 4.45 mole H, 7597,297,296,4--hydrocarbon 25
0.4 0.4 3.6 --H snow 0
--2.4 2.4--100 mol/Hr
1096 857 106B44 488Lb/l
(r carbon -1111111 stainless steel -11--------- Water vapor---a, axi o3 storm head hydrocarbon on carbon-------1 ----- 1 (, o------111-1 temperature, ? 85 200 20.11 110
582 Flow MSCF/D 2.5 3.5 2.1 -
---Morti H,3,23,2i2 ----Hydrocarbon type 9
6.896.8 96.8-1--I(, O------
--- Mol/Hr 252 38+ 226 ---
--L b /Hr Carbon ------1,2X10' 1.2X1
0” Stainless steel -------〇, 5X1050.5
X105 Water vapor ---11-------- Insects on carbon 1-hydrocarbon ---1--5,21,lH2O----
--t2 3.8 Temperature, "I? 110 117 117 390
400 flow molch H2---97,2------ Hydrocarbon type---0,4---H2O----
-2,4---100 mol/Hr---837---394L b
/Hr Carbon (IXlo") 1.2 1.2 -- t
2 12 -- Heavy carbon water damage on carbon 0.4 0.4 -- 7.1
9.6 --HxOO,30,3--------++ 7 crystallinity, lower 300 200 200 265 29
0 486 The method of the present invention has primary application in VC for the separation and recovery of hydrogen from mixtures with hydrocarbon systems contaminated with various acidic, polar or non-polar compounds other than hydrocarbons. up to about 50% or more hydrocarbons, preferably about 10 to about 50% hydrocarbons, and further mixed with, for example, carbon monoxide, carbon dioxide, Selected high-purity hydrogen can be easily recovered from hydrogen gas mixed with contaminants such as mercaptans, mercaptans, and the like.

Adsorbent solids can be conveniently used as mixtures or composites containing magnetic (ferrimagnetic or ferromagnetic) components or substances.

An example of this kind of magnetic material is magnetic Fe1O4, γ-iron oxide (F ex 04 )%MO-Fa203 where M is a gold coat such as Zn, Mn, Cu, etc., or a mixture thereof.] ferrite in the form of ferrite, or alloys of magnetic elements, magnetic iron, containing iron, nickel, cobalt and gadium. The adsorbent solid is selected to be appropriate for the particular feed and contaminant to be removed from the feed. Inorganic, organic or diurnal inorganic or organic adsorbents can be used.

Examples of adsorbent solids are activated carbon, treated activated carbon, molecular sieve carbon 5 selected synthetic zeolites, such as those containing some amount of certain synthetic zeolites, such as "Type A", "
L type” 1 “X type”, “Y type”, “28M type” 5 mordenite, 7 augiasite.

Zeolites containing some of the main components identified as erionite, such as zeolites with specific silica-alumina ratios, and those in which the original sodium cations have been exchanged with other cations, have been selected. Silica gels, such as those containing specific relative components of silica, alumina and ferric oxide, average pore size.

Those with specific steric properties such as specific area and pore volume, selected l-occupied aluminas, such as those with specific components of alumina oxide and water, those of hydrated type, those of hooked crystal type, An example of a clay with a specific structure, activated clay or selectively acidic clay, is montmorillonite (in which case the substrate is exchanged holoizite or attapulgite). Other suitable zeolites and methods of making them are described, for example, in U.S. Pat.
No. 3.13f1,007, No. 4410,808, No. 3,733.390, No. 3.827; Other adsorbents suitable for the practice of this invention, which are mentioned herein for reference, include benzenesulfonic acid, carboxylic acid,! Cation exchange resins having exchange groups such as acids; strong or weakly basic anion exchange resins; polymeric main particles of styrene-divinylbenzene copolymers or halomethylated or cyano-ethylated polymers thereof; acrylonitrile copolymers, e.g. contains several functional groups such as cyanogen, cyanomethyl, chloromethyl, thioether, sulfone, isocyanate, thiocyanate, thiourea, allyl, acetyl-acetone, aldehyde, ketone, lIC1 group, anhydride, ester, halogen, nitro, etc. It includes cylinder molecule parking 8'+lIJ.

Suitable adsorbents to achieve high adsorption-adsorption rates are t-occupied charcoal, molecular sieve charcoal, 5-synthetic zeolite, and sieved organic materials. These adsorbents generally exhibit adsorption exchange rates based on their chemical affinity for the adsorption of various contaminants. Synthetic zeolites are a particularly useful class of inorganic adsorbents. Therefore, the adsorption power of the molecules selected for adsorption onto zeolites is determined by the exchange of the sodium ions normally obtained from the original manufacturing process with other cations to shape their crystal structure or deuteron configuration into the desired shape. This is because it can be easily changed by changing it. Usually, for example lithium,
1st like potassium, rubidium, cesium, silver, copper
metal ions of the group; examples include beryllium, magnesium,
Group 2 metal ions such as calcium, strontium, barium, zinc, gadmium, hydroxide; titanium, vanadium, chromium, nickel, cobal), iron, manganese;
Rare earth metals; uranium; and lead cations or mixtures thereof are used to replace the sodium ions originally contained in the zeolite. Potassium and lithium; potassium and calcium; potassium and cadmium; potassium and iron; potassium and nickel; potassium and cobalt; potassium and barium; potassium and magnesium; calcium and magnesium; calcium and manganese; lithium and manganese; barium and sodium; barium and lead; iron and uranium. Synthetic zeolite adsorbent solids typically contain 75 to 98 zeolite components and 2 to 25 matrix (eg, binder) components.

Typically, the zeolite will be exchanged with sufficient cations to reduce the sodium level of the zeolite to below 511, preferably below 11. In this connection, reference may be made to the following U.S. specifications: No. 140.249, No. 140,251, No. 3.14.
No. 0.252 and No. 3,140.253, which are incorporated herein by reference.

When a magnetizable component is mixed with non-magnetic adsorbent particles, the volume fraction of the magnetizable component should preferably exceed 25% by volume, and more preferably exceed 50% by volume. , more preferably a 60 volume smoker, to obtain maximum bed stability with minimum applied magnetic field strength.

In the case of a composite of magnetizable component and adsorbent, the magnetic ferromagnetic (ferromagnetic and/or) ferrimagnetic material accounts for about 1% to about 25%, preferably about 5% of the total volume of the composite adsorbent. ~15%.

In any case, the composite should have a magnetic field of at least 50 Gauss, preferably 250 Gauss or higher.

A composite of a magnetizable component and an adsorbent can be prepared as follows: magnetic component particles, such as 400 series stainless steel, and an adsorbent, such as a zeolite sieve, are combined into a substrate for the adsorbent ( matrix or binder) to form a relatively homogeneous gel. The adsorbent substrate can be composed of silica, alumina or silica-alumina, for example. The gel is then dried, fired and sized. Suitable techniques for sizing and shaping the composite adsorbent include extrusion, billing, beading, and spray drying. The magnetizable component can also be complexed with the adsorbent by impregnation, co-gelation, co-precipitation, etc.

The bed particles (composite or mixture) typically have an average particle size in the range of about 50 to about 1500 microns, preferably about 100 to about 1000 microns, more preferably about 175 to about 850 microns. The particles may be of any shape, for example spherical, irregularly shaped or elongated.

The method of applying a magnetic field to fluidized, expanded or suspended particles containing nitrifiable particles in an adsorption or desorption zone according to the present invention is not limited to the particular method of generating the magnetic field.

Conventional permanent magnets may also be used to provide the magnetic fields used in the practice of the present invention. Determining the position of the magnet is of course important.

It will vary depending on the solid used, the fluidization inhibition required and the desired effect. Typically, toroidal electromagnets are used to surround at least a portion of the moving bed. This is because this provides the most uniform magnetic field across the bed and therefore the best stability. Electromagnets can be energized by alternating current or both currents, but
A flow-energized magnetic field is preferred. A partial magnet when energized by direct current using a rheostat is particularly desirable for applying a magnetic field to the bed particles and is an excellent choice for stabilizing the fluidization of the bed particles in response to the flow of the fluidizing medium. Give the method.

The magnets can be of any size, strength or shape, and can be placed above or below the floor for special effects. The magnets used can be placed inside or outside the container, and can also be used as an integral part of the container structure itself. The method is not limited to particular container materials and can be adapted to containers for use with contact containers currently in commercial use.

The field gate to be applied to the fluidized solid in the contacting zone (adsorption and desorption zone) will, of course, depend on the desired magnetization and the desired degree of stabilization for the magnetizable particles. Particles with relatively weak magnetic properties, such as cobalt, nickel, etc., require the application of a stronger magnetic field than particulate solids with strong magnetic ferrous properties, such as iron, to obtain an equivalent stabilizing effect. The size and shape of the solid will also obviously influence the strength of the magnetic field that should be used. However, since the strength of the magnetic field generated by the electromagnet can be adjusted by adjusting the magnetic field strength of the electromagnet, the strength of the W1% used can be easily adjusted to achieve the desired degree of stability for the particular system being used. can be achieved. A specific method for applying a magnetic field is described in U.S. Patent No. 5.440.731.
No., @ 5.439.899, No. 4.115.927
No. 4,143,469, British Patent No. 1,148
, No. 515, as well as published literature, parables, MVC, Applied Magnetohydrodynamics (Trudy Inatituka F.
izlka Akad, Nauk,.

Latviigkoi 5SR), g vol. 12, pp. 215-236 (1960); Ivanov et al., Kfne
t, Kavel, Volume 11(5), Nos. 1214-12
19 (1970); Ivanov et al., Zhurnal P.
r1kladnoi Khimii, Volume 45, No. 2
pp. 48-252 (1972); and R. E. Rosenwijk, Science, Vol. 204, No. 57-60.
(1979) K, which are incorporated herein by reference. 'The most preferably applied magnetic field would be a homogeneous magnetic field, such as that described in US Pat. No. 4,115,927. Typically, the total vessel applied magnetic field as taught in U.S. Pat. No. 4,115,927 is from about 50 to about 1500 Oersteds.

Preferably it will range from about 100 to about 600 oersteds, with a percentage preferably from about 125 to about 400 oersteds.

Water-based feeds can be provided using feed from each Yuzu source, such as catalytic pyrolysis flue gas, gas from catalytic reforming, etc.

It will be obvious that the invention is susceptible to modifications and alterations without departing from its spirit and scope.

[Brief explanation of the drawing]

The drawing is a flowchart schematically illustrating the method of the invention. 10: Apparatus 11: Cooling section 12: Adsorption section 15: Water-based substitution section 14: Desorption section 15 Varnish dripping section 16: Water removal section 1 Name of agent: Motohiro Kurauchi, : Akira Kurauchi 1' 7 10 Continuing from page 1 [phase] Inventor Grove G.A. Balinski 12 36 Mallory Avenue, Baton Rouche, Louisiana, U.S.A. @ Inventor Steven Ackerman Randolph Number H, New Chassis, U.S.A. 35 Center Grove Road 44

Claims (12)

[Claims] (1) Particulate adsorbent solids are used in the recovery of hydrogen from hydrogen-containing steam or gaseous feeds, either alone or in admixture with non-hydrocarbon components or with one or more hydrocarbon components. an adsorption zone for contacting the feed; a desorption zone operating at a temperature sufficiently above the temperature of the adsorption zone to desorb hydrocarbons selectively adsorbed onto the solid; and (7) I! 1, whereby said particulate adsorbent solids are porous and then cooled and recycled to said adsorption zone, said feed being moved downward in said adsorption zone (a). in countercurrent contact with a fluidized bed of particulate adsorbent solids, the adsorbent solids being provided with a magnetic component to magnetically stabilize said bed and inhibit large circulation of adsorbent solids within said bed; Hydrocarbons are selectively adsorbed from the feed onto the granular adsorbent solids, with the feed trap flowing into the magnetically stabilized adsorption zone containing more hydrogen content and less hydrocarbon gas. withdrawing from the adsorption zone a gas stream consisting of;
Hydrocarbon-enriched hydrogen-containing particulate adsorbent solids are withdrawn from the previous adsorption zone and transferred to a water bed displacement zone (b), where said hydrocarbon-enriched hydrogen-containing particulate adsorption It.
The solids are flowed in a plug flow and countercurrently contacted with sufficient hydrocarbon gas to substantially expel hydrogen from the MiJ water-containing solids, and the expelled hydrogen is transferred to an adsorption zone to transfer the dehydrogenated hydrocarbon-containing solids to the adsorption zone. (7) A zero adsorption method for recovering hydrogen, characterized in that particulate adsorbed solids are taken out from the hydrogen displacement zone (b) and transferred to the desorption zone (e). (2) Forming the dehydrogenated hydrocarbon-containing particulate adsorbent solids into a fluidized bed to be transferred to the desorption zone <c+ and heating to a temperature sufficient to desorb the hydrocarbons from the particulate solids, and desorbing the dehydrogenated hydrocarbons. removing hydrocarbons from said zone;
Particulate adsorbent solids containing at least a residual amount of hydrocarbons are transferred to an IJ stripping zone (d) and formed as a moving fluidized bed of said solids, which are then brought into countercurrent contact with a stripping agent. 2. A method as claimed in claim 1, characterized in that the residual hydrocarbons are desorbed and substantially discharged. (3) Claim 2, characterized in that the stripping agent is hydrogen and the stripping zone (d) is a hydrogen stripping zone. The method described in OiJ. (4) The stripping zone (d) is a steam stripping zone, the stripping agent is steam, and the moving bed further contains at least a residual amount of a hydrocarbon system. countercurrent contact with water vapor in the water removal zone (e) to substantially displace residual hydrocarbons with water vapor, and then contact the particulate adsorbent solids containing water vapor with the aqueous system in a water removal zone (e) to discharge the water. At the same time, after drying the granular adsorbent solid and recovering the aqueous system, the dried granular adsorbent solid is cooled in a cooling zone (f), and the cooled adsorbent solid is transferred to the adsorption zone. The method according to claim 2. (5) Adsorption flowing into either the hydrogen 1F exchange zone (b) or the desorption zone (e) or the IJ Zubing zone (d) or the water removal zone (.) or the cooling zone (f) or all of these zones. The method according to any one of claims 1 to 4, characterized in that the agent solid is fluidized and stabilized by applying & in a field. (6) Process according to claim 4, characterized in that the cooling zone (f) contains a fluidized bed of regenerated granular adsorbent solids in heat exchange relationship with a cooling fluid. (7) The temperature of the adsorption zone (a) is in the range of about 40 to about 300"F, and the zero temperature of the hydrogen displacement zone (b) is about 10 to about 150"F higher than the temperature of the adsorption zone.
7. The method according to any one of claims 1 to 6, characterized in that it is in the I+ range. (8) 0 adsorbent solids in the hydrogen displacement zone (b),
7. The method of claim 1, further comprising maintaining a bottom temperature of about 60 to about 450 degrees below the top (7) temperature of the bed. (9) Desorption zone (c) temperature is about 300 to about (SOO”)
F'7) range, and the hydrocarbon stripping zone (d
9. A method according to any one of claims 1 to 8, characterized in that the process is carried out at a temperature in the range from about 600 to below about 600 °C. (10) the water removal zone (e) is staged to bring the adsorbent particles into countercurrent contact with a proportion of hydrogen substantially equal to the volume of water vapor in the interstices and pores to substantially desorb water vapor; #-F, characterized in that it includes a first stage and a second stage in which the IA distilled water is desorbed by self-current contact with hydrogen, and the adsorbent particles are evaporated and cooled and dried.
The method described in any one of Items 4 to 9 O of the Scope of Tsumugi. (11) Claims 1 to 10, characterized in that the adsorbent particles and the magnetizable component are a composite body]
Any of the methods described above. (12) The drawings and examples are shown in %K Adsorption method for recovery.